Dyeing with a trifluoromethylphenylazo-8-quinolinol and articles so dyed



DYEING WITH A TRIFLUOROMETHYL- PHENYLAZO-S-QUINOLINOL AND AR- TICLES SO DYED Ernest M. May, Summit, and Andrew Fouo, Montclair, NJ., assignors to Otto B. May, Inc., Newark, N.J.,- a corporation of New Jersey I No Drawing. Original application Mar. 26, 1963, Ser. No.

267,948. Divided and this applicationgFeb. 11, 1965, Ser. No. 438,154

16 Claims. (Cl. 8-121) This is a division'of S.N. 267;9 48/ filed:Mar"26, 1963, and now Patent No. 3,222,350. i I

p This invention relates to new dyes and, more: partic ularly, it is concerned with compounds'whichi'a're especially suitable for dyeing shaped articles of polyolefins, such as polypropylene, and other hydrophobic thermoplastic resins, such as polyesters, polyacrylicsfandfpolyamides. p I 1 Many known classes of dyes have been applied to polypropylene and other polyolefins in an attempt to dye thesema'terials in a commercially satisfactory way, that is to say, to yield a dyed product which is fast to washing and dry cleaning. Those classes of dyes which are water-soluble are for this very reason unsuitable for dyeing polypropylene. The water solubility of these dyes means inherently that they are insoluble in polypropylene, and even if a surface dyeing is achieved they are readily removed by washing. Furthermore, the dyes Which are soluble in polypropylene (a fundamentally hydrocarbon polymer) are also soluble in dry cleaning solvents and those dyes which have affinity for polypropylene are generally removed by dry cleaning solvents.

An object of the present invention is to obtain dye compositions which are suitable for dyeing polypropylene and other polyolefins.

Another object of the invention is to obtain dyes which can be used for dyeing other thermoplastic resins, such as polyesters, polyacrylics, cellulose triacetate and polyamides.

It is common practice in the textile industry to form composite fabrics containing wool and a synthetic thermoplastic polymeric resin. For example, a composite fabric maybe woven of threads containing, in a predetermined pattern, threads of wool and polypropylene or some other thermoplastic fiber. In the past, many classes of dyes have been applied to these composite fabrics to give a union" dyeing. In other words, both the wool and the thermoplastic fiber are dyed to the same hue using normal dyeing procedures. However, this is unsuitable in certain commercial aspects where it is desired to dye the thermoplastic fiber in the composite fabric without dyeing the wool fiber therein.

Accordingly, another object of this invention is to provide a composite mixed fabric of wool fibers and polyolefin, e.g. polypropylene, fibers or other thermoplastic fibers and to produce dyes which will dye the thermoplastic fibers therein and which will not substantially stain or dye the wool therein employing the usual dyeing techniques.

'A further object of the present invention is to provide dyes which are fast to washing and severe dry cleaning when applied to synthetic shaped articles, particularly fibers containing finely dispersed metallic compounds.

One of the very difiicult problems that has confronted the industry is stabilizing polypropylene and other polyolefin fibers against aging, that is degradation caused by ice exposure to air, light, and/ or heat. Many types of known stabilizers have been incorporated into the fibers to impart some degree of stability thereto. However, these stabilizers generally are removedby washing and/or dry cleaning with various solvents, and the fibers lose most or all of their resistance to aging.

Accordingly, still another object of this invention, is to stabilize shaped articles formed from polypropylene.

stabilize and pigment such articles.

Another object is to improve stability and the resistance of these polymersy to aging, particularly after they have been washed, drycleaned or exposed to other solvents.

Other objects and advantages of the present invention will appear from the following description.

' The dyes which according to the present invention have been found to be particularly suitable for dyeing polypropylene andother polyolefins, are certain substituted monoazo 8-fi1uinolinol compounds described by the following structural formula:

and other polyolefins and preferably simultaneously wherein X is'a substituent group attached to the benzene nucleus selected from the group consisting of fluorine and trifluorornethyl; Y is a substituent group attached to the benzene nucleus selected from the group consisting of fluorine, ;;trifluoromethyl, hydrogen, chlorine, bromine, and methyl; and Z is selected from the group consisting of hydrogen and methyl. Other substituent groups for the benzene rings besides those indicated above are not within the scope of the present invention.

The aforementioned monoazo dyes can be prepared by any known method. However, they are generally formed by coupling a substituted aniline through diazotization with a 8- quinolinol. A finely dispersed paste is preferably formed-from the resulting dyestuff, for example, by milling in the presence of a dispersing agent.

In one embodiment, a synthetic shaped article, for example, a fiber, has a metal incorporated therein before a substituted 8-quinoliuol compound is applied. In another embodiment of the present invention, the synthetic fiber is notmodified with a metallic material. The unmodified or modified synthetic fibers or other shaped articles applicable to this invention include polyolefins, polyesters, for example, condensation products of polybasic acids with polyhydric alcohols and Dacron; polyamides, such as nylon; polymers of acrylic acid compounds, such as acrylonitrile; polymers of vinyl compounds, such as vinyl alcohol, vinyl chloride and styrene; poly-acetals, such as polyformaldehyde; and cellulose triacetate. A polyolefin, which is a preferred polymer for a synthetic fiber, includes the following polymers among others: polyethylene, polypropylene, polybutene, poly-3-methyl-butene-1, polypentene, poly-4-methyl-pentene-1, and polyheptene, The polyolefin, e.g,, polypropylene, can be prepared by any known method.

Synthetic shaped articles are formed from one or more of the aforementioned thermoplastic olymers or from one or more of these polymers in combination with wool as a composite fabric in accordance with known prior art procedures. A fiber, which is preferred, is defined herein as any fibrous unit, for instance, filament yarns, mats,

staple yarns, rovings, sheets, rods, plates, woven fabrics and chopped fibers. The following exemplify specific commercial fibers which can be employed herein: Spun Dacron T-54, manufactured by E. I. du Pont de Nemours & Co., Inc.; Nylon Filament Thread, manufactured by E. I. du Pont de Nemours & Co., Inc.; Cresland T58; Acrilan 1656; Polypropylene 805 Fiber, manufactured by Reeves Brothers, Inc.; and Arnel, manufactured by Celanese Corporation of America.

The substituted monoazo S-quinolinol dye compounds heretofore described form the basis of an aqueous dye bath into which the fibers are immersed. Since the dyes are insoluble in water, they must be dispersed in the bath. Any known dyeing technique may be employed in this invention, including the methods discussed and referenced in the article by Fortess, Advances in Textile Processing, vol. 1, pages 333-373, to provide a dyed fiber therefrom.

As stated heretofore, the synthetic shaped article, e.g., a fiber, may be modified with a metallic material. As defined in this invention, a metal modified synthetic shaped article is one which contains additional metal therein besides the metal that may be present as residual catalyst from the preparation of the synthetic thermoplastic polymer itself. This added metal in the fiber forms a reaction product with the subsequently applied dye composition. Although the precise nature and structure of the aforementioned reaction product is not clearly" understood, it is possible that a chelate ring or linkage is formed between the metallic cation and the hydroxyl group on the 8- quinolinol ring. However, the amountof dye employed for the reaction with the metal and the ratio of fiber to metal are not critical features of this invention.

Any suitable metal or more than one metal may be incorporated into the synthetic fiber or other shaped article. Aluminum, nickel, chromium and zinc are the preferred metals, and they are utilized as metallic compounds. Organic metal salts, for example, may be employed within the range of .02 to .2% based upon the weight of the fiber. Carboxylic acid metal salts with 6 to 20 carbon atoms, which are preferred for this invention, include aluminum stearate, zinc stearate, aluminum laurate, the aluminum salt of Z-ethyl hexanoic acid and mixtures thereof.

The fiber may be modified with the aforementioned metallic materials by any satisfactory method. A satisfactory, but not the only, method (as disclosed in Belgian Pat. No. 617,280 which is incorporated herein by reference) is to disperse intimately an. organic metal salt throughout the polymer at any stage prior to its extrusion. An eflicient blending apparatus is usually adequate to accomplish this result. After dispersion the blend may be extruded at the fluid temperature for the polymer, i.e., 250 to 350 C. for polypropylene. Accordingly, the metal is usually distributed uniformly throughout the fiber, e.g. polyolefin fiber, which provides complete penetration of the dye from the dye bath into the fibers. By way of illustration, the incorporation of the metal salt in the polymer may be made by mixing parts of the powder of the salt with 90 parts of the powder of the polymer to an intimate and uniformly dispersed mixture. This mixture may be extruded to form a concentrate which subsequently is finely divided again and intimately blended with additional polymer to obtain the desired low concentration of metal for extrusion to the shaped product.

In is also within the purview of this invention to react the aforementioned substituted monoazo 8-quinolinol compound with the metallic material in solution without any shaped article, such as fiber, being present. A pigment is formed thereby which can be recovered and used as a pigment in a manner known in the art.

Thus, in accordance with the instant invention substituted monoazo 8-quinolinol compounds have been provided which are suitable dyestuffs. For example, these compounds will react with metal-modified shaped articles to form a dyed end product which is fast to light,

dry cleaning and washing. Similarly, these compounds can be applied directly to dye an unmodified fiber since, for example, nylon, polyester, cellulose triacetate and acrylic fibers have polar groups which can form a polar linkage with the present dyes to improve the receptivity of the dye and the fastness properties.

The superior light fastness of the dye on the metalmodified or unmodified shaped article is a first surprising feature of this invention. Secondly, it is surprising that the instant substituted monoazo 8-quinolinol compounds also impart stability to the polyolefin fibers and other shaped articles and resist removal by laundering, dry cleaning and the like. A third surprising feature is the fact that dye compounds with two or more substituent groups on a benzene ring are soluble in polypropylene or other polyolefin fibers. Fourthly, it is indeed unexpected and surprising that if a composite, mixed fiber of wool and a thermoplastic polymer, such as polypropylene, is placed in the usual aqueous dye bath with the instant substituted monoazo 8-quinolinol compounds therein, the thermoplastic polymer portion in the composite fabric is dyed but the wool portion in the composite fabric is substantially undyed.

The following examples are submitted to illustrate but not to limit this invention. Unless otherwise indicated, all parts and percentages in the specification are based upon weight.

' EXAMPLE I A 5-(2-trifiuoromethylbenzeneazo)-8-quinolinol dyestutf was provided by dissolving 16.1 parts of orthoaminobenzotrifiuoride in 200 parts of water containing 34.2 parts concentrated hydrochloric acid. After stirring until completely dissolved, the solution therefrom was cooled to 0-5 C., and it was added all at once to a solution of 7 parts sodium nitrite in 35 parts of water. The resulting first solution was stirred one-half hour and then clarified by filtration.

A separate and second solution was formed consisting of 14.5 parts 8-quinolinol in 500 parts of water containing 8.5 parts of 50% sodium hydroxide. This second solution was kept at a temperature of 50 C. for one-half hour; the pH was adjusted with acetic acid to 7, and 49.5 parts of sodium acetate were then added with subsequent cooling to 30 C.

The first solution was then added to the second solution until a negative test for 8-quinolinol was obtained. The dyestutf therefrom was filtered off and finely dispersed.

Fiber grade polypropylene, which was blended intimately and uniformly with 0.080 wt. percent of aluminum monostearate, was used to manufacture 4 /2 denier crimped staple fiber by melt extruding, stretching, crimping, and cutting to a 2 in. length. This cut fiber was subsequently carded and spun to produce yarns approximating .1-0s single (cotton system) count. Convenient sized skeins were then reeled from this yarn.

A sample containing ten grams of skein was provided. This sample was immersed in a 500 cc. dye bath at 120 F. The bath consisted of an aqueous dispersion of 0.6 gram of the dry aforementioned dyestuif. Prior to the entry of the yarn, sufficient acetic acid was added to the dye bath to provide a pH of 6.0. The dyeing was accomplished by gradually raising the temperature of the dye bath to its boiling point during a 30 minute period. The skein was frequently turned with a glass stirring rod and the temperature was maintained at 212 F. for a period of one hour. The yarn was then removed from the dye bath and thoroughly rinsed in running water at 160 F. The skein was subsequently scoured by turning it for 30 minutes at 160 F. in a 400 cc. aqueous bath containing /2% of triton X- (iso-octyl-phenyl poly-ethoxy ethanol) and /z% of sodium carbonate. A thorough rinse was subsequently performed in running water at F.

The dyed sample was then subjected to the following tests.

(1) Color fastness to dry cleaning: Tentative Test Method 85-1960 (1960 Technical Manual of the American Association of Textile Chemists and Colorists, pages 88-9) amended as follows: the temperature shall be 115 F.; the time shall be 1 hour; and the amount of perchlorethylene shall be 200 cc.

(2) Color fastness to washing (polypropylene): Tentative Test Method 61-1960, test number III-A (1960 Technical Manual of the American Association of Textile Chemists and Colorists, pages 93-4). In each instance the dyeings shall rate (for polypropylene) as follows: for color loss, class for staining, class 3 or better.

(3) Color fastness for washing (synthetics): AATCC tentative test method 61-1961 T (page 105 c. cit.) with Test III-A being used for polyester and afterchromed nylon and Test II-A for nylon.

(4) Color fastness to light: AATCC Standard Test Method l6-A-l960 (page 9010c. cit.).

(5) Color fastness to oxides of nitrogen in the atmosphere: Three cycles were used of Standard Test Method 23-1957 (page '98 10c. cit.) or Standard Test Method 75-1956 (page 100 loc. cit.).

(6) Sublimation and heat fastness tests: Sublimation and Heat Fastness tests were run at 265 F. for minutes.

The dyed polypropylene had a yellow shade with outstanding light fastness.

EXAMPLE II A Dacron fiber was dyed with the dye of Example I by providing a bath of 180 F. containing 200 parts water and 1.5 parts of a blend of 67% biphenyl and 33% anionic emulsifier. Ten grams of skein were incorporated for a five to ten minute run. The aforementioned dye,

EXAMPLE III The compounds indicated in Table I include the dye described in the previous examples and those dyes which were prepared by comparable procedure-s with the reactants being varied to form the desired end product. Polypropylene fibers were dyed with each of the compounds as per Example I to the shades indicated in Table I. All of the dyed products had excellent fastness to light.

TABLE I Dye N0. A-Ring Shade Substitutes 1, 2-CF Yellow. 2 4-15 Do. 3 a D0. 4 3-CF fi-Cl Do.

Having set forth the general nature and specific embodiments of the present invention, the scope is now particularly pointed out in the appended claims.

We claim:

1. An article which comprises a synthetic shaped article dyed and stabilized with a compound which is S-(Z-trifluoromethylbenzeneazo)-8-quinolinol, 5-(4-trifluoromethylbenzeneazo)-8-quinolinol or 5-(3-trifluoromethyl-6-chlorobenzeneazo)-8-quinolinol.

2. An article which comprises a synthetic shaped article dyed with the reaction product formed between a metallic material and a dye which is 5-(Z-trifluoromethylbenzeneazo) 8 quinolinol, 5-(4 trifiuoromethylbenzeneazo)-8- quinolinol or 5-(3-trifluoromethyl-6-chlorobenzeneazo)-8- quinolinol.

3. A process which comprises preparing a substituted monoazo S-quinolin-ol compound which is 5-(2-trifluoromethylbenzeneazo)-8-quinolinol, 5-(4-trifluoromethylbenzeneazo) 8 quinolinol or 5-(3-trifluoromethyl-6-chlorobenZeneazo)-8-quinolinol; and applying said substituted monoazo 8-quinolinol compound to provide a dyed synthetic shaped article having excellent fastness properties and good stability-properties.

4. A process which comprises preparing a substituted monoazo 8-quinolinol compound which is 5-(2-trifluoromethylbenzeneazo)-8-quinolinol, 5-(4-trifluoromethylbenzeneazo) 8 quinolinol or 5-(3-trifluorornethyl-6-chlorobenzeneazo)-8-quinolinol; modifying a synthetic shaped article independently with a metallic material; and applying said substituted monoazo 8-quinolinol compound to said modified shaped article to provide a dyed shaped article having excellent fastness properties.

5. A composite shaped article which comprises a thermoplastic polymer fiber and wool; said shaped article having had applied thereto a compound which is 5-(2-trifluoromethylbenzeneazo)-8-quinolinol, 5-(4-trifiuoromethylbenzeneazo)-8-quinolinol or 5-(3-trifluoro-6-chlorobenzeneazo)-8-quinolino1; said thermoplastic polymer fiber in said shaped article being dyed with said compound; said wool in said shaped article being substantially undyed.

6. A process which comprises preparing a substituted monoazo 8-quinolinol compound which is 5-(2-trifluoromethylbenzeneazo)-8-quinolinol, 5-(4-trifluoromethylbenzeneazo)-8-quinolinol or 5-(3-trifluoro-6-chlorobenzeneaZo)-8-quinolinol; forming independently a composite shaped article comprising a thermoplastic polymer fiber and wool; and applying said monoazo compound to said shaped article to dye the thermoplastic polymer fiber therein without dyeing the wool therein.

7. The article according to claim 1 in which the shaped article is a synthetic fiber.

8. The article according to claim 7 in which the synthetic fiber is a polymer selected from the group consisting of polyolefins, polyesters, polyamides, polymers of acrylic acid compounds, polymers of vinyl compounds, polyacetals and cellulose triacetate.

9. The article according to claim 8 in which the polymer is polypropylene.

10. The article according to claim 2 in which the shaped article is a poly-olefin shaped article.

11. The article according to claim 3 in which the shaped article is a polypropylene shaped article.

12. The article according to claim 2 in which the metal in the metallic material is selected from the group consisting of aluminum, nickel, chromium, zinc and mixtures thereof.

13. The article which comprises a polypropylene fiber dyed with the reaction product formed between aluminum monostearate and 5-(2-trifluoromethylbenzeneazo)- 8-quinolinol.

14. An article which comprises a polyester fiber dyed with 5-(Z-trifluoromethylbenzeneazo)-8-quinolinol.

15. An article which comprises a polypropylene fiber dyed with the reaction product formed between aluminum monostearate and 5-(4-trifluoromethylbenzeneazo-)- 8-quinolinol.

16. An article which comprises a polypropylene fiber dyed with the reaction product formed between alumi- 7 8 num monostearate and 5-(3-trifluoromethyl-6-Ch1oroben- OTHER REFERENCES 9 Vankataraman: The Chemistry of Synthetic Dyes; vol- References Cited lxlfnggclg taage 1221, pub. 1952 by Academic Press Inc. New

1 y. UNITED STATES PATENTS 5 Hopf: Chimia, v01. 15, January 1961, pages 193-194. 2,868,774 1/1959 Straley et a1 8-55 2,984,634 5/1961 Caldwell et a1 8-55 DONALD LEVY, Primary Examiner.

3,186,788 6/1965 Mills 842 

1. AN ARTICLE WHICH COMPRISES A SYNTHETIC SHAPED ARTICLE DYED AND STABILIZED WITH A COMPOUND WHICH IS 5-(2-TRIFLUOROMETHYLBENZENEAZO)-8-QUINOLINOL, 5-(4-TRIFLUOROMETHYLBENZENEAZO)-8-QUINOLINOL OR 5-(3-TRIFLUOROMETHYL-6-CHLOROBENZENEAZO)-8-QUINOLINOL. 